We report a new method for the preparation of a wide range of linear poliynes, la-li, with an odd number of C^C bonds. This method is based on solution-spray flash vacuum pyrolysis (SS-FVP) of the readily available 3,4-dialkynyl-3cyclobutene-l,2-diones 3a-3i. It allows the synthesis of multigram quantities of a series of hexatriynes and decapentaynes from poorly volatile and thermally unstable precursors that cannot be subjected to conventional flash vacuum pyrolysis. Yields of the linear poliynes range from 42 to 99%. Similarly, the dodecahexayne lj was obtained in 31% yield by SS-FVP of the bis(3-cyclobutene-l,2-dione) 3j. The synthesis of the new 3,4-dialkynyl-3-cyclobutene-l,2-diones 3h-3j via the ketals 7, 10, and 13 is reported. The X-ray crystal structure of l,10-diphenyl-l,3,5,7,9-decapentayne (lc) was solved, and the crystal packing structure provides valuable information to explain the thermal polymerization behavior observed for this compound in the
The field of micro- and nanofabrication has developed extensively in the past several decades with rising interest in alternative fabrication techniques. Growth of these areas has been driven by needs that remain unaddressed by traditional lithographical methods: inexpensive, upscalable, biocompatible, and easily integrated into complete lab-on-a-chip (LOC) systems. Shape memory polymers (SMPs) have been explored as an alternative substrate. This review first focuses on structure fabrication at the micron and nanoscale using specifically heat-shrinkable SMPs and highlights the innovative improvements to this technology in the past several years. The second part of the review illustrates demonstrated applications of these micro- and nanostructures fabricated from heat-shrinkable SMP films. The review concludes with a discussion about future prospects of heat-shrinkable SMP structures for integration into LOC systems.
Dense multiscale silica (SiO2) micro‐ and nanostructures are fabricated on a pre‐stressed polymer film. This novel SiO2 substrate serves as a robust platform to enhance the fluorescence signal of bound biomolecules. Through a combination of surface concentration, light scattering, and changes in the photophysical properties of the confined dye molecules, dramatic fluorescence signal enhancements (average = 116 times greater than on planar glass) and increased signal‐to‐noise ratio (76:1) are demonstrated with tetramethylrhodamine isothiocyanate (TRITC)‐conjugated streptavidin (STRITC) on SiO2 structures. Enhanced detection sensitivity of STRITC over glass on the SiO2 structures is achieved down to a detection limit of 11 ng mL−1. Such significant fluorescence signal enhancements have importance in practical applications such disease diagnostics and surface sensing.
We describe a manufacturable and
scalable method for fabrication
of multiscale wrinkled silica (SiO2) structures on shrink-wrap
film to enhance fluorescence signals in DNA fluorescence microarrays.
We are able to enhance the fluorescence signal of hybridized DNA by
more than 120 fold relative to a planar glass slide. Notably, our
substrate has improved detection sensitivity (280 pM) relative to
planar glass slide (11 nM). Furthermore, this is accompanied by a
30–45 times improvement in the signal-to-noise ratio (SNR).
Unlike metal enhanced fluorescence (MEF) based enhancements, this
is a far-field and uniform effect based on surface concentration and
photophysical effects from the nano- to microscale SiO2 structures. Notably, the photophysical effects contribute an almost
2.5 fold enhancement over the concentration effects alone. Therefore,
this simple and robust method offers an efficient technique to enhance
the detection capabilities of fluorescence based DNA microarrays.
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